US5498651A - Method for polymerizing macrocyclic polyester oligomers - Google Patents
Method for polymerizing macrocyclic polyester oligomers Download PDFInfo
- Publication number
- US5498651A US5498651A US08/497,694 US49769495A US5498651A US 5498651 A US5498651 A US 5498651A US 49769495 A US49769495 A US 49769495A US 5498651 A US5498651 A US 5498651A
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- US
- United States
- Prior art keywords
- accordance
- oligomers
- group
- macrocyclic polyester
- poly
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired - Lifetime
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Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G63/00—Macromolecular compounds obtained by reactions forming a carboxylic ester link in the main chain of the macromolecule
- C08G63/02—Polyesters derived from hydroxycarboxylic acids or from polycarboxylic acids and polyhydroxy compounds
- C08G63/12—Polyesters derived from hydroxycarboxylic acids or from polycarboxylic acids and polyhydroxy compounds derived from polycarboxylic acids and polyhydroxy compounds
- C08G63/40—Polyesters derived from ester-forming derivatives of polycarboxylic acids or of polyhydroxy compounds, other than from esters thereof
- C08G63/42—Cyclic ethers; Cyclic carbonates; Cyclic sulfites; Cyclic orthoesters
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G63/00—Macromolecular compounds obtained by reactions forming a carboxylic ester link in the main chain of the macromolecule
- C08G63/91—Polymers modified by chemical after-treatment
- C08G63/914—Polymers modified by chemical after-treatment derived from polycarboxylic acids and polyhydroxy compounds
- C08G63/916—Dicarboxylic acids and dihydroxy compounds
Definitions
- the instant invention is directed to a process for making polyesters.
- the process employs epoxides or episulfides which unexpectedly result in improved polymerization of molten macrocyclic polyester oligomers.
- Polyesters such as poly(alkylene terephthalates) are well known commercially available polymers. They have valuable characteristics including strength, toughness, high gloss and solvent resistance. Polyesters are commercially prepared by the reaction of diols with functional derivatives of dicarboxylic acids, diacid halides or esters. Further, the above-described polyesters may be fabricated into articles by a number of well known techniques including injection and roto molding and extrusion.
- macrocyclic polyester oligomers have been developed and desired since they have unique properties which make them attractive as matrices for polymer composites.
- the desired properties stem from the fact that macrocyclic polyester oligomers exhibit low viscosities when compared to those of corresponding polymers. Such low viscosities allow them to easily impregnate dense fibrous preforms.
- polyesters are prepared by contacting macrocyclic polyester oligomers and a polymerization catalyst at a temperature within the range of about 160°-300° C.
- the instant invention is directed to a process for making polyesters comprising the step of contacting in the presence of at least one compound selected from the group consisting of epoxides and episulfides:
- the macrocyclic polyester oligomers which may be employed in this invention are preferably macrocyclic poly(alkylene dicarboxylate) oligomers comprising structural units of the formula ##STR1## wherein R is an alkylene or mono- or polyoxyalkylene radical containing a straight chain of about 2-8 atoms and A is a m- or p-linked monocyclic aromatic or alicyclic radical.
- R is an alkylene or mono- or polyoxyalkylene radical containing a straight chain of about 2-8 atoms
- A is a m- or p-linked monocyclic aromatic or alicyclic radical.
- the macrocyclic polyester oligomers are of the family consisting of polymeric glycol terephthalates or isophthalates and mixtures thereof including copolyesters of terephthalic and isophthalic acids. They are typically characterized by an Mn value of less than about 1500 but preferably about 300 to about 800.
- oligomers employed in the instant invention are macrocyclic poly(1,2-ethylene 2,6-naphthalene dicarboxylate) (PEN), poly(ethylene terephthalate) (PET) and poly (1,4-butylene terephthalate) (PBT) oligomers and copolyesters comprising the same.
- PEN macrocyclic poly(1,2-ethylene 2,6-naphthalene dicarboxylate)
- PET poly(ethylene terephthalate)
- PBT poly (1,4-butylene terephthalate)
- the oligomers may be prepared by a method which comprises contacting at least one diol of the formula HO--R--OH and at least one diacid chloride of the formula ##STR2## under substantially anhydrous conditions and in the presence of a substantially water immiscible organic solvent, with at least one unhindered tertiary amine; said contact being conducted at a temperature from about -25° to about +25° C.
- reagents used to synthesize the macrocyclic poly(alkylene dicarboxylate) oligomers employed in the instant invention include unhindered tertiary amines and substantially water-immiscible organic solvents.
- a detailed description for the preparation of the above-mentioned macrocyclic polyester oligomers employed in this invention may be found in commonly assigned U.S. Pat. No. 5,039,783, the disclosure of which is incorporated herein by reference.
- catalysts which may be employed in this invention are those which are capable of enhancing the polymerization of the macrocyclic polyester oligomers described above.
- the often employed catalysts include organotin compounds and titanate catalysts.
- organotin compounds are dialkyltin(IV) oxides such as di-n-butyltin(IV) oxide and di-n-octyltin oxide and acyclic and cyclic dialkyltin(IV) dialkoxides such as di-n-butyltin(IV) di-n-butoxide and 2,2-di-n-butyl-2-stanna-1,3-dioxacycloheptane tributyltin ethoxide.
- Illustrative titanate catalysts include isopropyl titanate, 2-ethylhexyl titanate, and tetrakis-(2-ethylhexyl)titanate.
- Epoxides which may be employed in this invention include, for example, non-halogenated and halogenated alkylene oxides like oxirane, propylene oxide, epichloro-, epifluoro- and epibromohydrin, compounds with epoxy groups attached to cyclic residues like cyclohexane oxide and related cycloaliphatic resins, terminal epoxides like glycidyl compounds and epoxides of ⁇ -olefins and compounds with non-terminal epoxy groups attached to noncyclic carbon chains.
- epoxides which may be employed in this invention include aliphatic diepoxides such as dodecatriene dioxide, dipentene dioxide and 1,2,7,8-diepoxyoctane; bis-glycidyl ethers/esters such as the bisglycidyl ether of bisphenol A and its condensation products; alicyclic diepoxides such as 3,4-epoxycyclohexyl 3,4-epoxycyclohexanecarboxylate and bis(3,4-epoxycyclohexylmethyl) adipate; mixed aliphatic/alicyclic diepoxides such as vinylcyclobutene dioxide, vinylcyclopentadiene dioxide and butenylcyclopentene dioxide; glycidyl ethers of novolak resins; epoxidized heterocycles such as triglycidyl isocyanurate; and epoxidized oils such as epoxidized tall oil, linseed oil and soybean
- Still other epoxides which may be employed in this invention include, for example, alicyclic epoxides which may be hindered, less-hindered or unhindered as defined in The Determination of Epoxide Groups, B. Dobinson et al., Pergamon Press, 1969.
- thio analogs of the epoxides described above wherein thio analog is defined herein to mean the oxygen of the epoxide is replaced with sulfur.
- epoxidation co-catalysts like tetrabutylphosphonium bromide in this invention.
- each A is independently ##STR3## and each R is independently a hydrogen, halogen, hydroxy group, alkoxy group, C 1-10 hydrocarbon or substituted or unsubstituted aromatic radical and Z is oxygen or sulfur.
- B is a divalent bridging radical or group, wherein the divalent bridging radical is not limited and often a substituted or unsubstituted --C-- or alicyclic or aromatic radical and the bridging group is not limited and often a substituted or unsubstituted polycyclic, polyaromatic or aliphatic group.
- Said bridging group may also be a member having the formulae ##STR4## wherein R is as previously defined and each q is independently about 0 to about 30 and often 0 or 1.
- the often preferred epoxide employed in this invention is commercially available and is 3,4-epoxycyclohexyl 3,4-epoxycyclohexylcarboxylate.
- a reaction vessel When conducting the instant novel method, a reaction vessel may be charged with the macrocyclic polyester oligomers, polymerization catalysts and epoxide and/or episulfide and their order of addition is not material. Heat is supplied to melt the oligomers (about 135° C. to about 250° C.) for polymerization and stirring may be employed under an inert gas in order to enhance the polymerization of the oligomers to produce the desired polymer. Additionally, the epoxides and polymerization catalysts employed in this invention may first be dissolved in a solvent such as o-dichlorobenzene in order to enhance mixing.
- a solvent such as o-dichlorobenzene
- the amount of epoxides and/or thioepoxides employed in this invention are often about 0.01 to about 3.0 mole % and preferably about 0.02 to about 1.0 mole % and most preferably about 0.1 to about 0.25 mole % based on total moles of monomer units of oligomer.
- the amount of polymerization catalyst employed in this invention is often about 0.01 to about 5.0 mole % and preferably about 0.02 to about 2.0 mole % and most preferably about 0.2 to about 0.5 mole % based on total moles of monomer units of oligomer.
- the desired polyesters produced in this invention often include poly(ethylene terephthalate), poly(1,4-butylene terephthalate), poly(1,2-ethylene 2,6-naphthalene dicarboxylate) and copolyesters comprising the same.
- a 25 mL flask was charged with 5.0 g of macrocyclic copolyester oligomer (PET/PBT, 5% by wt. PET).
- the oligomer was heated at 100° C. in an oil bath under vacuum for about 10 minutes and at 190° C. for an additional 10 minutes. Vacuum was released, and the oligomer was completely molten.
- To the molten oligomer was added 46 ⁇ L of a 1.0M solution of 3,4-epoxycyclohexyl 3,4-epoxycyclohexylcarboxylate and o-dichlorobenzene (0.20 mole % epoxy).
- the resulting mixture was stirred for about 5 minutes after which 69 ⁇ L of a 1M solution of tetrakis-(2-ethylhexyl)titanate and O-dichlorobenzene (0.30 mole % titanate) were added.
- the mixtrure with titanate was stirred and crystalline polymer formed within 10 seconds.
- the flask was removed from the oil bath and was broken to retrieve a sample of polymer.
- the polymer was dissolved in a solution of 15% hexafluoroisopropanol and 85% chloroform. GPC analysis of the resulting solution unexpectedly showed 96.4% polymerization.
- Example 2 was prepared in a manner similar to the one described in Example 1 except that 23 ⁇ L of a 1.0M epoxy solution (0.10% epoxy) was used and the co-polyester oligomer/epoxy mixture was stirred for 24 hours at 190° C. after which the polymerization catalyst was added. Heating continued for an additional 40 minutes after which the catalyst addition and GPC analysis of the resulting polymer unexpectedly showed 97.0% polymerization of macrocyclic oligomer.
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- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Polyesters Or Polycarbonates (AREA)
Abstract
Description
TABLE ______________________________________ % Poly- merization % Poly- Entry.sup.ab % Epoxide Catalyst merization Mw.sup.d ______________________________________ 1 None .sup.c 39.5 61,300/1,382.sup.e 2 None .sup.c 53.4 38,900/1,350.sup.e 3 0.20% .sup.c 96.4 352,300 4 0.25% .sup.c 92.3 75,200 5 None .sup.c 47.5 48,800 6 None .sup.i 99.0 144,000 7 1.0% .sup.c 99.5 81,000 8 0.50% .sup.i 99.0 138,000 9 0.50%.sup.f .sup.i 98.0 121,700 10 0.25% .sup.c 100.0 215,900 11 0.25%.sup.g .sup.c 78.3 78,900 12 0.10% .sup.c 97.0 246,000 13 None.sup.h .sup.c 61.0 96,000 ______________________________________ .sup.a Entries 1-4, crude PET/PBT cocyclic, polymerizations at 190.degree C. for 40 minutes. .sup.b Entries 5-8 and 10-12, purified PET/PBT cocyclic, held molten at 190° C. for 24 hours, polymerization after catalyst addition. .sup.c 0.30 mole % tetrakis(2-ethylhexyl)titanate. .sup.d Average weight molecular weight based on polystyrene standards. .sup.e Bimodal. .sup.f Purified PET/PBT cocyclic, held molten at 175° C. for 24 hours, polymerization after catalyst addition. .sup.g 0.0025% tetrabutylphosphonium bromide epoxidation cocatalyst. .sup.h Purified PET/PBT cocyclic, dioctylphthalate plasticizer additive t decrease melt temperature, held molten at 175° C. for 24 hours, polymerization after catalyst addition. .sup.i 0.50 mole % tributyltin ethoxide.
Claims (12)
Priority Applications (5)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
US08/497,694 US5498651A (en) | 1995-06-19 | 1995-06-19 | Method for polymerizing macrocyclic polyester oligomers |
EP96302451A EP0749999B1 (en) | 1995-06-19 | 1996-04-04 | Method for polymerizing macrocyclic polyester oligomers |
DE69611269T DE69611269T2 (en) | 1995-06-19 | 1996-04-04 | Process for polymerizing macrocyclic polyester oligomers |
ES96302451T ES2153937T3 (en) | 1995-06-19 | 1996-04-04 | PROCEDURE FOR THE POLYMERIZATION OF MACROCICLIC POLYESTER OLIGOMERS. |
JP09162096A JP3510952B2 (en) | 1995-06-19 | 1996-04-15 | Polymerization method of macrocyclic polyester oligomer |
Applications Claiming Priority (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
US08/497,694 US5498651A (en) | 1995-06-19 | 1995-06-19 | Method for polymerizing macrocyclic polyester oligomers |
Publications (1)
Publication Number | Publication Date |
---|---|
US5498651A true US5498651A (en) | 1996-03-12 |
Family
ID=23977932
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
US08/497,694 Expired - Lifetime US5498651A (en) | 1995-06-19 | 1995-06-19 | Method for polymerizing macrocyclic polyester oligomers |
Country Status (5)
Country | Link |
---|---|
US (1) | US5498651A (en) |
EP (1) | EP0749999B1 (en) |
JP (1) | JP3510952B2 (en) |
DE (1) | DE69611269T2 (en) |
ES (1) | ES2153937T3 (en) |
Cited By (32)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US6229420B1 (en) * | 1996-06-05 | 2001-05-08 | Siemens Aktiengesellschaft | Proximity switches with mechanical decoupling of connection pins and connection insert |
US6369157B1 (en) | 2000-01-21 | 2002-04-09 | Cyclics Corporation | Blend material including macrocyclic polyester oligomers and processes for polymerizing the same |
US6420048B1 (en) | 2001-06-05 | 2002-07-16 | Cyclics Corporation | High molecular weight copolyesters from macrocyclic oligoesters and cyclic esters |
US6420047B2 (en) | 2000-01-21 | 2002-07-16 | Cyclics Corporation | Macrocyclic polyester oligomers and processes for polymerizing the same |
US6436548B1 (en) | 2000-09-12 | 2002-08-20 | Cyclics Corporation | Species modification in macrocyclic polyester oligomers, and compositions prepared thereby |
US6436549B1 (en) | 2001-07-16 | 2002-08-20 | Cyclics Corporation | Block copolymers from macrocyclic oligoesters and dihydroxyl-functionalized polymers |
US6525164B2 (en) | 2000-09-01 | 2003-02-25 | Cyclics Corporation | Methods for converting linear polyesters to macrocyclic oligoester compositions and macrocyclic oligoesters |
US20030094725A1 (en) * | 2001-06-14 | 2003-05-22 | Fuji Xerox Co., Ltd. | Polymer compound, process for producing the same, molded article and process for producing the same |
US6599991B1 (en) * | 1999-12-30 | 2003-07-29 | Eastman Kodak Company | In-situ blending of polyesters with poly(ether imide) |
WO2003080705A1 (en) * | 2002-03-20 | 2003-10-02 | Cyclics Corporation | Catalytic systems |
US20040106713A1 (en) * | 2002-12-03 | 2004-06-03 | Avakian Roger W. | Use of additives in compounds containing macrocyclic poly(alkylene dicarboxylate) oligomers |
US6787632B2 (en) | 2001-10-09 | 2004-09-07 | Cyclics Corporation | Organo-titanate catalysts for preparing pure macrocyclic oligoesters |
US20040192879A1 (en) * | 2002-12-20 | 2004-09-30 | Phelps Peter D. | Purification of macrocyclic oligoesters |
US20040220334A1 (en) * | 2000-01-21 | 2004-11-04 | Yi-Feng Wang | Blends containing macrocyclic polyester oligomer and high molecular weight polymer |
US20040225058A1 (en) * | 2000-01-21 | 2004-11-11 | Tohru Takekoshi | Intimate physical mixtures containing macrocyclic polyester oligomer and filler |
US6831138B2 (en) | 2002-01-07 | 2004-12-14 | Cyclics Corporation | Polymer-containing organo-metal catalysts |
US20040254281A1 (en) * | 2001-06-27 | 2004-12-16 | Thompson Timothy A | Isolation, formulation and shaping of macrocyclic oligoesters |
US20050059768A1 (en) * | 2002-12-20 | 2005-03-17 | Dion Robert P. | Polymerized macrocyclic oligomer nanocomposite compositions |
US20050137333A1 (en) * | 2003-12-19 | 2005-06-23 | Cyclics Corporation | Processes for dispersing an impact modifier in a macrocyclic polyester oligomer |
US20050282952A1 (en) * | 2000-01-21 | 2005-12-22 | Cyclics Corporation | Graphite-polyester composites made from macrocyclic polyester oligomers |
US20050288420A1 (en) * | 2004-06-18 | 2005-12-29 | Paquette Michael S | Method for preparing reactive formulations of macrocyclic oligomers |
US20060003887A1 (en) * | 2004-06-18 | 2006-01-05 | Paquette Michael S | Catalyst-containing clay materials for composites in polymer of macrocyclic oligomers |
US20060004135A1 (en) * | 2004-06-18 | 2006-01-05 | Paquette Michael S | Polymerizable macrocyclic oligomer masterbatches containing dispersed fillers |
US20060115666A1 (en) * | 2000-01-21 | 2006-06-01 | Cyclics Corporation | Methods for polymerizing macrocyclic polyester oligomers using catalyst promoters |
US20060148963A1 (en) * | 2002-12-23 | 2006-07-06 | Dion Robert P | Electrically conductive polymerized macrocyclic oligomer carbon nanofiber compositions |
EP1679341A1 (en) * | 2005-01-11 | 2006-07-12 | Sika Technology AG | Impact resistant composition |
US20060194946A1 (en) * | 2001-06-27 | 2006-08-31 | Cyclics Corporation | Processes for shaping macrocyclic oligoesters |
US20060235185A1 (en) * | 2000-09-01 | 2006-10-19 | Cyclics Corporation | Preparation of low-acid polyalkylene terephthalate and preparation of macrocyclic polyester oligomer therefrom |
US20080289758A1 (en) * | 2004-03-24 | 2008-11-27 | The Dow Chemical Company | Reactive Hot Melt Adhesive |
US20090264548A1 (en) * | 2004-10-25 | 2009-10-22 | Van Der Wal Hanno R | Polyurethanes made from hydroxy-methyl containing fatty acids or alkyl esters of such fatty acids |
US7750109B2 (en) | 2000-09-01 | 2010-07-06 | Cyclics Corporation | Use of a residual oligomer recyclate in the production of macrocyclic polyester oligomer |
US10471655B2 (en) | 2015-09-04 | 2019-11-12 | Carbon, Inc. | Cyanate ester dual resins for additive manufacturing |
Families Citing this family (3)
Publication number | Priority date | Publication date | Assignee | Title |
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JP2002363301A (en) * | 2001-06-11 | 2002-12-18 | Toyobo Co Ltd | Polyester molding |
US20050095415A1 (en) * | 2003-10-30 | 2005-05-05 | Raghavendran Venkat K. | Glass mat thermoplastic composite |
WO2010148188A2 (en) * | 2009-06-19 | 2010-12-23 | Polyone Corporation | Oxygen scavenging terpolymers |
Citations (2)
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US5039783A (en) * | 1990-11-05 | 1991-08-13 | General Electric Company | Method for preparing and polymerizing macrocyclic poly(alkylene discarboxylate) oligomers |
US5387666A (en) * | 1994-06-20 | 1995-02-07 | General Electric Company | Branched polyesters prepared from macrocyclic poly(Alkylene Dicarboxylate) oligomers |
Family Cites Families (1)
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AT265646B (en) * | 1965-02-25 | 1968-10-25 | Metallgesellschaft Ag | Process for increasing the molecular weight of a fiber and film-forming polyester |
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1995
- 1995-06-19 US US08/497,694 patent/US5498651A/en not_active Expired - Lifetime
-
1996
- 1996-04-04 DE DE69611269T patent/DE69611269T2/en not_active Expired - Fee Related
- 1996-04-04 ES ES96302451T patent/ES2153937T3/en not_active Expired - Lifetime
- 1996-04-04 EP EP96302451A patent/EP0749999B1/en not_active Expired - Lifetime
- 1996-04-15 JP JP09162096A patent/JP3510952B2/en not_active Expired - Fee Related
Patent Citations (2)
Publication number | Priority date | Publication date | Assignee | Title |
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US5039783A (en) * | 1990-11-05 | 1991-08-13 | General Electric Company | Method for preparing and polymerizing macrocyclic poly(alkylene discarboxylate) oligomers |
US5387666A (en) * | 1994-06-20 | 1995-02-07 | General Electric Company | Branched polyesters prepared from macrocyclic poly(Alkylene Dicarboxylate) oligomers |
Cited By (64)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US6229420B1 (en) * | 1996-06-05 | 2001-05-08 | Siemens Aktiengesellschaft | Proximity switches with mechanical decoupling of connection pins and connection insert |
US6599991B1 (en) * | 1999-12-30 | 2003-07-29 | Eastman Kodak Company | In-situ blending of polyesters with poly(ether imide) |
US20060115666A1 (en) * | 2000-01-21 | 2006-06-01 | Cyclics Corporation | Methods for polymerizing macrocyclic polyester oligomers using catalyst promoters |
US20050245676A1 (en) * | 2000-01-21 | 2005-11-03 | Cyclics Corporation | Macrocyclic polyester oligomers and processes for polymerizing the same |
US20040225058A1 (en) * | 2000-01-21 | 2004-11-11 | Tohru Takekoshi | Intimate physical mixtures containing macrocyclic polyester oligomer and filler |
US6994914B2 (en) | 2000-01-21 | 2006-02-07 | Cyclics Corporation | Macrocyclic polyester oligomers and processes for polymerizing the same |
US20040220334A1 (en) * | 2000-01-21 | 2004-11-04 | Yi-Feng Wang | Blends containing macrocyclic polyester oligomer and high molecular weight polymer |
US20050282952A1 (en) * | 2000-01-21 | 2005-12-22 | Cyclics Corporation | Graphite-polyester composites made from macrocyclic polyester oligomers |
US20060122307A1 (en) * | 2000-01-21 | 2006-06-08 | Cyclics Corporation | Intimate physical mixtures containing macrocyclic polyester oligomer and filler |
US6420047B2 (en) | 2000-01-21 | 2002-07-16 | Cyclics Corporation | Macrocyclic polyester oligomers and processes for polymerizing the same |
US7151143B2 (en) | 2000-01-21 | 2006-12-19 | Cyclics Corporation | Blends containing macrocyclic polyester oligomer and high molecular weight polymer |
US6639009B2 (en) | 2000-01-21 | 2003-10-28 | Cyclis Corporation | Macrocyclic polyester oligomers and processes for polymerizing the same |
US6960626B2 (en) | 2000-01-21 | 2005-11-01 | Cyclics Corporation | Intimate physical mixtures containing macrocyclic polyester oligomer and filler |
US20040011992A1 (en) * | 2000-01-21 | 2004-01-22 | Cyclics Corporation | Macrocyclic polyester oligomers and processes for polymerizing the same |
US7230044B2 (en) | 2000-01-21 | 2007-06-12 | Cyclics Corporation | Intimate physical mixtures containing macrocyclic polyester oligomer and filler |
US6369157B1 (en) | 2000-01-21 | 2002-04-09 | Cyclics Corporation | Blend material including macrocyclic polyester oligomers and processes for polymerizing the same |
US20060235185A1 (en) * | 2000-09-01 | 2006-10-19 | Cyclics Corporation | Preparation of low-acid polyalkylene terephthalate and preparation of macrocyclic polyester oligomer therefrom |
US20080214775A1 (en) * | 2000-09-01 | 2008-09-04 | Cyclics Corporation | Methods for converting linear polyesters to macrocyclic oligoester compositions and macrocyclic oligoesters |
US8283437B2 (en) | 2000-09-01 | 2012-10-09 | Cyclics Corporation | Preparation of low-acid polyalkylene terephthalate and preparation of macrocyclic polyester oligomer therefrom |
US6525164B2 (en) | 2000-09-01 | 2003-02-25 | Cyclics Corporation | Methods for converting linear polyesters to macrocyclic oligoester compositions and macrocyclic oligoesters |
US20060128936A1 (en) * | 2000-09-01 | 2006-06-15 | Cyclics Corporation | Methods for converting linear polyesters to macrocyclic oligoester compositions and macrocyclic oligoesters |
US20030236386A1 (en) * | 2000-09-01 | 2003-12-25 | Faler Gary R. | Methods for converting linear polyesters to macrocyclic oligoester compositions and macrocyclic oligoesters |
US6855798B2 (en) | 2000-09-01 | 2005-02-15 | Cyclics Corporation | Methods for converting linear polyesters to macrocyclic oligoester compositions and macrocyclic oligoesters |
US20050176917A1 (en) * | 2000-09-01 | 2005-08-11 | Cyclics Corporation | Methods for converting linear polyesters to macrocyclic oligoester compositions and macrocyclic oligoesters |
US7767781B2 (en) | 2000-09-01 | 2010-08-03 | Cyclics Corporation | Preparation of low-acid polyalkylene terephthalate and preparation of macrocyclic polyester oligomer therefrom |
US7750109B2 (en) | 2000-09-01 | 2010-07-06 | Cyclics Corporation | Use of a residual oligomer recyclate in the production of macrocyclic polyester oligomer |
US6436548B1 (en) | 2000-09-12 | 2002-08-20 | Cyclics Corporation | Species modification in macrocyclic polyester oligomers, and compositions prepared thereby |
US6713601B2 (en) | 2000-09-12 | 2004-03-30 | Cyclics Corporation | Species modification in macrocyclic polyester oligomers, and compositions prepared thereby |
US6420048B1 (en) | 2001-06-05 | 2002-07-16 | Cyclics Corporation | High molecular weight copolyesters from macrocyclic oligoesters and cyclic esters |
US20030094725A1 (en) * | 2001-06-14 | 2003-05-22 | Fuji Xerox Co., Ltd. | Polymer compound, process for producing the same, molded article and process for producing the same |
US7056988B2 (en) * | 2001-06-14 | 2006-06-06 | Fuji Xerox Co., Ltd. | Polymer compound, process for producing the same, molded article and process for producing the same |
US20060194946A1 (en) * | 2001-06-27 | 2006-08-31 | Cyclics Corporation | Processes for shaping macrocyclic oligoesters |
US20070037464A1 (en) * | 2001-06-27 | 2007-02-15 | Cyclics Corporation | Isolation, formulation, and shaping of macrocyclic oligoesters |
US7666517B2 (en) | 2001-06-27 | 2010-02-23 | Cyclics Corporation | Isolation, formulation, and shaping of macrocyclic oligoesters |
US20040254281A1 (en) * | 2001-06-27 | 2004-12-16 | Thompson Timothy A | Isolation, formulation and shaping of macrocyclic oligoesters |
US7071291B2 (en) | 2001-06-27 | 2006-07-04 | Cyclics Corporation | Isolation, formulation and shaping of macrocyclic oligoesters |
US6436549B1 (en) | 2001-07-16 | 2002-08-20 | Cyclics Corporation | Block copolymers from macrocyclic oligoesters and dihydroxyl-functionalized polymers |
US6787632B2 (en) | 2001-10-09 | 2004-09-07 | Cyclics Corporation | Organo-titanate catalysts for preparing pure macrocyclic oligoesters |
US20050054862A1 (en) * | 2001-10-09 | 2005-03-10 | Cyclics Corporation | Organo-titanate catalysts for preparing pure macrocyclic oligoesters |
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US20050227861A1 (en) * | 2002-03-20 | 2005-10-13 | Cyclics Corporation | Catalytic systems |
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ES2153937T3 (en) | 2001-03-16 |
JPH093178A (en) | 1997-01-07 |
DE69611269T2 (en) | 2001-04-26 |
EP0749999A3 (en) | 1997-07-30 |
EP0749999A2 (en) | 1996-12-27 |
DE69611269D1 (en) | 2001-01-25 |
EP0749999B1 (en) | 2000-12-20 |
JP3510952B2 (en) | 2004-03-29 |
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